2882
J. Am. Chem. SOC.1981, 103, 2882-2884
except for bands at 1538 and 1240 cm-’. We tentatively assign these bands to the symmetric and antisymmetric W-H-W vibrationsZ2of confacial bioctahedral W2ClsH3-. These bands are absent when the reaction is run in concentrated aqueous DCl and are replaced by new bands at 1120 and 896 cm-’. Dissolution of the mixture in aqueous HCl produced hydrogen and clean conversion (by UV spectroscopy) to w2c193(eq 5 ) . 2 5 3
+
5HCI
+ 3CI-
IHC I
X-ray quality crystals of unsolvated 3 have not yet been isolated, but we have prepared and crystallized (by vacuum sublimation) a diglyme adduct of 3. The structure of Wz(0zCCF3)4-z/3(CH30CH2CH20CH2CH20CH3) was determined from diffraction data collected at -160 0C.z7 A view of the structure, which emphasizes the “tridentate” naturez9 of the diglyme, is shown in Figure 1. Tungsten dimers A and B are crystallographically independent and are in the same unit cell as the p ~ l y e t h e r . Tungsten ~~ dimer B’ is related to B by a unit translation. As anticipated, each W2(TFA)4molecule has idealized D4h symmetry with the tungsten atoms bridged by trifluoroacetate ligands. The W-W bond lengths are 2.211 (2) and 2.207 (2) 8, for dimers A and B, respectively. The axial solvent oxygen contacts with the dimers vary from 2.48 (1) to 2.70 (1) 8, (see Figure 1). Full details of the structure will be reported elsewhere. The results presented here clearly demonstrate that quadruply bonded tungsten(I1) carboxylate complexes are isolable and stable in the absence of potential oxidizing agents. We believe that they will serve as valuable synthetic intermediates in dimeric tungsten(I1) chemistry. Further elaboration of the chemistry and physical properties of tungsten(I1) carboxylates will be reported in the near future.
mass spectrometer used in this research was purchased, in part, by funds provided by the National Science Foundation. Supplementary Material Available: The solid-state Raman spectra of M o ~ ( O ~ C C Fand ~ ) ~W2(OzCCF3)4and tables of fractional coordinates and thermal parameters (3 pages). Ordering information is given on any current masthead page.
Palladium-Catalyzed Stereo- and Regiospecific Cou ling of Allylic Derivatives with Alkenyl- and Arylmetals! A Highly Selective Synthesis of 1,4-Dienes Hajime Matsushitat and Ei-ichi Negishi* Department of Chemistry, Purdue University Lafayette, Indiana 47907 Received December 22, I980 We wish to describe a remarkably facile and highly selective Pd-catalyzed cross-coupling reaction2 of alkenylmetals containing A1 or Zr with allylic halides or acetates, which not only proceeds with essentially complete retention of the stereo- and regiochemistry of both alkenyl and allyl groups but is free from the formation of the homocoupled products. When used in conjunction with hydroal~mination,~ hydrozirconation: or carboaluminationS of acetylenes, the reaction provides a uniquely expeditious route to 1 , 4 - d i e n e ~(eq ~ * ~1). We further report that the corresponding .R 3
L
R’ = carbon group; RZ= H or alkyl; R 3 and R4 = two hydrogens or two alkyl groups; M = A1 or Zr
+On leave from the Japan Tobacco & Salt Public Corp. (1) Selective Carbon-Carbon Bond Formation via Transition-Metal Catalysis. 18. Part 17: Yoshida, T.; Negishi, E. J . Am. Chem. Soc. 1981, 103, Acknowledgment. The Research Corporation and the donors 1276. of the Petroleum Research Fund, administered by the American (2) (a) For a review, see: Negishi, E. In “Aspects of Mechanism and Chemical Society, are acknowledged for support of this work. We Organometallic Chemistry”; Brewster, J. H.,Ed.; Plenum: New York, 1978; also thank the Marshall H. Wrubel Computing Center, Indiana p 285. (b) Negishi, E.; Baba, S. J . Chem. Soc., Chem. Commun. 1976, 596. (c) Baba, S.;Negishi, E. J . Am. Chem. SOC.1976,98,6729. (d) Negishi, E.; University, for a generous gift of computing time. The Finnegan King, A. 0.;Okukado, N. J . Org. Chem. 1977, 42, 1821. (e) King, A. 0.; Okukado, N.; Negishi, E. J. Chem. SOC.,Chem. Commun. 1977, 683. (f) (22) These vibrational assignments fit nicely with the data of Katovic and Negishi, E.; Van Horn, D. E. J. Am. Chem. SOC.1977,99, 3168. (g) OkuMcCarleyZ3on Mo2ClsH3-and MoWClaH3-. Essentially identical results are kado, N.; Van Horn, D. E.; Klima, W. L.; Negishi, E. TetrahedronLett. 1978, obtained with W2(mhp),‘ dissolved in concentrated aqueous HCI and DCL2‘ 1027. (h) Negishi, E.; Okukado, N.; King, A. 0.;Van Horn, D. E.; Spiegel, (23) Katovic, V.; McCarley, R. E. Znorg. Chem. 1978, 17, 1268-1270. B. I. Ibid. 1978, 100, 2254. (i) King, A. 0.;Negishi, E.; Villani, F. J., Jr.; (24) Sattelberger, A. P.; McLaughlin, K. W., unpublished results. Silveira, A,, Jr. J . Org. Chem. 1978, 43, 358. 6 ) Negishi, E.; Valente, L. F.; (25) Metathetical primary products such as W2Clsc or W2C17(H20)3-are Kobayashi, M. J . Am. Chem. SOC.1980, 102, 3298. (k) Kobayashi, M.; conceivable intermediates in this reaction, but we have no proof for their Negishi, E. J . Org. Chem. 1980, 45, 5223. existence. For a discussion of binuclear oxidative addition to molybdenum(3) Wilke, G.; Muller, H. Liebigs Ann. Chem. 1960, 629, 222. molybdenum quadruple bonds, see ref 26. (4) Wailes, P. C.; Weigold, H.; Bell, A. P. J . Orgunomet. Chem. 1971, 27, (26) Cotton, F. A.; Kalbacher, B. J. Znorg. Chem. 1976, 15 522-524. 373. See also: Hart, D. W.; Blackburn, T. F.; Schwartz, J. J . Am. Chem. (27) W2(TFA)4~2/~(~H30CH2CH20CH2CH20CH3) crystallizes in the SOC.1975, 97, 679. triclinic space group P1 with a = 23.046 (9), b = 9.108 (2), c = 9.222 (2) (5) Van Horn, D. E.; Negishi, E. J . Am. Chem. SOC.1978, 100, 2252. A; a = 99.64 ( l ) , B = 59.45 ( I ) , y = 103.55 ( 1 ) O ; V = 1617.9 AS;p (calcd) (6) The reactions of allylmetal derivatives with alkenyl halides are gen= 2.800 g for M,909.2 and Z = 3. Diffraction data were collected at erally nonstereoselective. For a review on the reaction of ?r-allylnickelcom-160 OC by a 8-28 scan technique with equipment described in detail elseplexes with organic halide, see: Semmelhack, M. F. Org. React. 1972, 19, where.28 Data were corrected for absorption ( H 110.35 cm-’) and the structure 117. was solved by a combination of Patterson, difference Fourier, and full-matrix (7) Stereo- and regiodefined alkenylmetals containing AI, B, and Cu have least-squares refinement techniques. All atoms, excluding diglyme hydrogen been shown to cross couple with allylic halides. The scope of the selective atoms, have been located and their positional and thermal parameters (analkenyl-allyl coupling involving AI and B is practically limited to y-unsubisotropic for W, C, 0, and F) refined. The current discrepancy indices are stituted allylic halides. Although the reactions of alkenylcoppers with allylic R = 0.047 and RWl= 0.046 for those 3486 reflections with F, t 3.0 o(F,). electrophiles are highly promising, examples of the reactions of stereodefined T i e limits of data collection were 6 I 28 I 45’ (Mo Ka radiation). alkenylcopperswith stereodefined allylic electrophilesappear to be essentially (28) Huffman, J. C.; Lewis, L. N.; Caulton, K. G. Inorg. Chem. 1980,19, unknown. AI: (a) Lynd, R. A,; Zweifel, G. Synthesis 1974, 658. (b) Baba, 2755-2762. S.; Van Horn, D. E.; Negishi, E. Tefrahedron Lett. 1976, 1927. (c) Eisch, (29) ( a ) The crystal structure29b of M O ~ ( O ~ C P ~ ) ~ . J.~ J.; - Damasevitz, G. A. J . Org. Chem. 1976, 41, 2214. (d) Uchida, K.; !CH30CH2CH20CH2CH20CH3)reveals two dilgyme molecules bound axUtimoto, K.; Nozaki, H. Zbid. 1976, 41, 2215. B: Yamamoto, Y.; Yatagai, ially to the molybdenum(I1) carboxylate in a monodentate fashion, Le., one H.; Sonoda, A.; Murahashi, S.-I. J . Chem. SOC.,Chem. Commun. 1976,452. methoxy oxygen from each solvent molecule binds to the dimer. The Mo-.O Cu: (a) Normant, J. F.; Bourgain, M. Tetrahedron Lett. 1971, 2583. (b) distance in this example is 2.633 (6) A. (b) Collins, D. M.; Cotton, F. A,; Corey, E. J.; Cane, D.; Libit, L. J . Am. Chem. SOC.1971, 93, 7016. (c) Murillo, C. A. Znorg. Chem. 1976, 15, 2950-2951. Raynolds, P. W.; Manning, M. J.; Swenton, J. S. J . Chem. Soc., Chem. (30) The symmetry related partner of tungsten dimer B has not been Commun. 1977,499. (d) Alexakis, A,; Cahiez, G.; Normant, J. F. Synthesis included in the drawing. 1979, 826.
0002-7863/81/1503-2882$01.25/0
0 1981 American Chemical Society
J . Am. Chem. Soc., Vol. 103, No. 10, 1981 2883
Communications to the Editor
A* Pd(PPhd4 15 mol THF
%I
PdlPPh3lq 15mol %) THF
reaction of arylmetals, such as those containing Zn, can also be markedly promoted by Pd catalysts, although that of simple alkylmetals, such as those containing AI or Zn, does not seem to be catalyzed by them. Consequently, the results herein reported significantly broaden the scope of the Pd-catalyzed allylation involving allylic electr~philes~~~ which has been essentially limited to the allylation of a few limited types of enolates8 and organometals containing highly electronegative metals.'O Specifically, (E)-(Zmethyl-1-octeny1)dimethylalane (l),prepared by the Zr-catalyzed carboal~mination~ of 1-octyne with Me3AI, reacts with 1 equiv of allyl bromide or isoprenyl chloride in THF under the influence of 5 mol % of Pd(PPh3)4to produce the expected cross-coupled products 2 and 3 in 90 and 98% yields, respectively. Significantly, each of these reaction mixtures displays essentially one GLC peak in the product region. In the absence of the Pd catalyst the yields of the cross-coupled products, after 1 h, are negligible (
